Mixed packet photographic emulsions using resin couplers



Jan. 4, 1955 L. GODOWSKY ET AL 2,693,797

MIXED PACKET PHOTOGRAPHIC EMULSIONS usmc RESIN COUPLERS Filed March 30, 1953 e E LATINO- RE COUPLER SILVER HALI DE EMULSION SILVER HAIJDE EM U LSION- RESIN COUPLE POLYMER CONTNN' SOLUTION ING SALT-FORMING EAARLrmAIdgFAL ACID GROUPS SALT ALKALINE EARTH METAL S A LT PARTICLES OF G E LATIN, SILVER HALIDE, RESIN COUPLER,

POLYMER, IN GELATIN MATRIX Ek$?N, SILVER HALIDE,

INSOLUBLE SALT OF RESIN COUPLER. IN GELATIN MATRIX Leopold Gallows/ y LouisM Minsk INVEN TORS AT TORII/[EYS' United States Patent MIXED PACKET PHOTOGRAPHIC EMULSIONS USING RESIN COUPLERS Leopold Godowsky, Westport, Conn., and Louis M. Minsk, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey Application March 30, 1953, Serial No. 345,626

14 Claims. (Cl. 95-2) This invention relates to color photography and particularly to mixed packet photographic emulsions.

There have been many prior suggestions of mixed grain photographic emulsions, that is, photographic systems in which differently sensitized silver halide grains are incorporated in a single photographic emulsion layer and used to produce differently colored photographic images in the layer. Mixed grain systems have a number of advantages, chief among which is the simplicity of coating a single emulsion layer rather than several layers. Other advantages are the improved definition obtained by having the differently sensitized particles juxtaposed in a single layer, and the simplification of processing which is generally obtained.

Godowsky U. S. application Serial No. 156,066, filed April 15, 1950, describes a mixed packet photographic color process in which the light-sensitive color-developable portion consists of packets suspended or dispersed in a continuous phase or matrix of gelatin or other hydrophilic water-permeable colloid. These packets are made by treating both a color sensitized silver halide gelatin emulsion and color forming components with a polymeric material referred to as a packet former, in the presence of another polymer or modifier which aids in packet formation. Additional gelatin or other vehicle may then be added to prepare the mixture for coating, and suitable packets similarly prepared but of different sensitivity and different color developability are then mixed and the mixture coated as a single layer. The system described in the Godowsky application requires a separate packet former and coupler; this is sometimes a disadvantage.

It is therefore an object of the present invention to provide an improved mixed packet photographic emulsion. A further object is to provide a mixed packet emulsion having improved definition and resolving power. Other obiects will appear from the following description of our invention.

These obiects are accomplished by forming in gelatin or similar hydrophilic colloid, a dispersion of packets or discrete particles produced by the interaction of the gelatin of a gelatino-silver halide emulsion, and a resincouoler combination of the composition described below, in the presence of either a water-soluble polymer containing salt-forming acid groups or a precipitant of such polymer, e. g., an alkaline earth metal salt, quaternary salt. amine salt, etc., of such polymer. Other dispersions of differently sensitive emulsion may then be mixed with the first dispersion The accompanying drawing is a flow sheet illustrating the steps in our process.

The resin couplers wh ch we propose to use havethe following recurring structure:

where R is hydrogen or a phenyl, alkyl, alkoxy, car boxyalkyl or acyloxy radical, x and y are 0 or 1, R represents a color-forming group capable of reacting with the oxidation product of a primary aromatic amino developing agent on photographic development, and R" is hydrogen or an alkyl radical, e. g., methyl or ethyl, said color-forming material containing an aryl group.

According to our invention, a solution of the sodium salt or other water-soluble salt of the resin-coupler 1s preferably first added to the silver halide emulsion, preferably a gelatino-silver chlorobromide emulsion, as shown in the three boxes at the top of the drawing and packets or discrete particles of emulsion and resin-coupler formed by adding to the combination of emulsion and resincoupler either (1) a water-soluble polymer or watersoluble salt of a polymer containing salt-forming acid groups, e. g. methyl-u-methacrylate-methacrylic acid, as shown in the left column of the drawing or (2) a solution of a precipitant for the resin coupler, preferably an alkaline earth metal salt, e. g. calcium acetate, as shown in the right column of the drawing.

According to the first method, the formation of packets is brought about by adding to the solution of silver halide emulsion and resin-coupler, a water solution of a watersoluble polymer or a water-soluble salt of a polymeric material containing salt-forming acid groups, such as the copolymer of methacrylic acid and methyl-a-methacrylate (Minsk, Weyerts and McDowell U. S. Patent 2,391,181), algin (alkali metal salt of polymeric-dmannuronic acid), carboxymethyl cellulose (Collins, Freeman and Anthonisen U. S. Patent 2,278,612), and cellulose sulfate (Belgian Patent 448,249), or the resincoupler may be added to a solution of the emulsion and water-soluble polymer or salt of the polymer.

According to the second method, the solution of silver halide emulsion and resin coupler and a solution of a polyvalent metal salt, a polyamine, a high molecular weight amine, or a high molecular weight quaternary salt, especially a solution of an alkaline earth metal salt, e. g., calcium, strontium or magnesium, are added slowly and simultaneously to a second solution of the alkaline earth metal salt. The alkaline earth metal ion forms a salt with the acid group of the resin coupler, and packets or particles of resin-coupler salt, gelatin and silver halide are formed. Additional gelatin is ordinarily added to complete the emulsion or dispersion of sensitive color-forming particles.

The formation of the packet emulsions will be described in the following examples.

Example 1 To 4.4 g. of a red-sensitive silver chlorobromide emulsion containing 80% by Weight silver chloride and having a gelatin content of 21.6 g. per mol of silver, there was added 44 cc. of water and the mixture stirred for 10 minutes at 40 C. To this emulsion, there was added 14 cc. of a 5% solution in water of the sodium s lt of the resin cou ler of Example 7 (pH about 7). This mixture was stirred for 20 minutes and 3 cc. of a -10% solution of the copolymer of methvl-a-methacrylate and methacrylic acid was added at pH 8. The solution was mixed for 25 minutes and 6 cc. of 10% magnesium sulfate solution was added to the mixture, stirred for 5 minutes more, and 25 cc. of 20% gelatin solution added.

Example 2 To 3.2 g. of a silver chlorobromide emulsion containing 2% by weight silver chloride and having a gelatin content of 21.0 g. per mol of silver, there was added 22 cc.

of water. and the mixture stirred for 10 minutes at 40 stirred for 25 minutes.

ring for 5 minutes, 25 cc. of 20% gelatin solution was added.

Example 3 To 4 g. of a green-sensitive gelatino-silver chlorobromide emulsion containing by weight silver chloride and having 8.7 g. of gelatin per mol of silver. there 9 was added 40 cc. of water and 3.3 g. of 20% phthalic anhydride gelatin (prepared by reacting 20 g. of phthalic anhydride with 100 g. of gelatin in the manner described in Example 1 of Yutzy and Frame U. S. Patent 2,525,753). To this emulsion there was added 7 cc. of a solution in water of the sodium salt of the resin coupler of Example 9. After stirring for 20 minutes, 2 cc. of a solution of the copolymer of methyl-a-methacrylate and methacrylic acid was added. When a good dispersion of the packets was obtained, 3 cc. of a 10% solution of magnesium sulfate was added, followed by cc. of a gelatin solution consisting of equal parts of bone gelatin and phthalic anhydride gelatin.

A mixed packet emulsion of two colors was made as follows:

Example 4 To 1 part of the emulsion of Example 2, there were added 2 parts of the emulsion of Example 1 with addition of the usual spreading agent and emulsion hardener. This mixed emulsion was coated on 5 x 7 glass plates, exposed under a step tablet and processed in a developing solution of the following composition to form a negative colored image.

Grams 2-amino-5-diethylamino toluene HCl 2 Sodium sulfite 2 Sodium carbonate 20 Potassium bromide 2 Water to one liter.

A mixed packet emulsion may also be made using the resin couplers of our invention, by precipitating the resin coupler and silver halide gelatin packet with heavy metal salt, without using the water-soluble polymers, such as methyl-u-methacrylate and methacrylic acid copolymer. This is illustrated by the following examples:

Example 5 To 30 cc. of a 4% solution of resin coupler prepared by the reaction of vinyl acetate-maleic anhydride interpolymer and 1-hydroxy-4-cl1loro-2-{3-aminoethyl naphthamide as described in Example 12, there was added sulficient dilute acetic acid to adjust the pH to 7 to 7.5. To this solution, there was added with stirring at 40 C., 3.5 g. of a red-sensitive gelatino-silver chlorobromide emulsion containing an 80% by weight silver chloride. This solution of silver halide emulsion and coupler, and 32 cc. of a 1% solution of calcium acetate were added slowly and simultaneously to 56 cc. of a 0.1% solution of calcium acetate over a period of /2 hour. Packets of emulsion and coupler formed during this addition, the

size and dispersion of the particles being partially depend- I Example 6 A dispersion of a green-sensitive magenta-forming emulsion was formed similarly to Example 5, using as the resin coupler, 15 cc. of a 4% solution of a resin coupler prepared from styrene-maleic anhydride interpolymer and l-p-aminophenol-3-butyramido-5-benzoxypyrazole as described in Example 14, and 2 g. of a green-sensitive gelatino-silver chlorobromide emulsion containing 80% by weight silver chloride. This solution and 16 cc. of a 2% solution of calcium acetate were added slowly and with stirring to 28 cc. of a 0.2% solution of calcium acetate to form the green-sensitive packet emulsion.

To form a mixed emulsion, 7.5 g. of each of the redsensitive and green-sensitive emulsions were mixed with 7.5 g. of 10% bone gelatin solution to which was added a dioctyl hydroquinone dispersion equal to 100 mg. of dioctyl hydroquinone. The mixed emulsion was coated at a rate of 12 cc. per 5 x 7 inch plate, dried, exposed through a color test chart, developed with the developing solution of Example 4, bleached and fixed in the usual manner.

Instead of using the packet emulsions of our invention to form a mixed packet layer, the packet emulsion may be used as a single layer emulsion on the usual photographic support, or one or more packet emulsions may be used as one of the layers of a multilayer photographic coating, for example, in a multilayer photographic material having superposed red-sensitive, green-sensitive and blue-sensitive silver halide emulsions.

The resin couplers which we use may also be incorporated directly in a silver halide emulsion without the 4 formation of packets, in the manner suggested by Fisher U. S. Patent 1,102,028.

Typical polymers which may be used in forming the resin couplers used according to our invention, and methods by which the polymers may be prepared, are as follows:

A. Polyacrylic anhydride having the recurring structure In an all-glass reflux outfit protected from moisture by a calcium chloride tube were placed 292 g. of acrylic anhydride, 2920 cc. of dry 1,4 dioxane, and 1.46 g. of benzoyl peroxide. The reaction mixture was heated on a steam bath for four hours during which time it turned to a white thick slurry. The precipitate was filtered on to a Buchner funnel, washed quickly with 1,4 dioxane and dried over calcium chloride in a vacuum desiccator under a constantly applied vacuum.

B. Interpolymer of vinyl acetate and maleic anhydride having the recurring structure In an all-glass reflux outfit protected from moisture by a calcium chloride tube were placed 196 g. of malcic anhydride, 172 g. of vinyl acetate, 7.4 g. of benzoyl peroxide, 4456 g. of dry benzene, and 44 g. of xylene. The reaction mixture was heated on a steam bath during which time it changed to a heavy slurry. Heating was continued for 1 /2 hours after the appearance of cloudiness. The precipitate was filtered, stirred twice with 2-liter portions of dry toluene followed by filtration after each extraction. The product was dried over calcium chloride in a vacuum desiccator under constantly applied vacuum followed by 20 hours at C. in an oven. The yield was 310 g. Inherent viscosity was 0.23. (See Cragg, J. Colloid Science, vol. 1, page 261, 1946, for description of inherent viscosity.)

C. Styrene-maleic anhydride interpolymer having the recurring structure The styrene-maleic anhydride interpolymer was prepared by the procedure described in Examples 2 and 3 of Godowsky U. S. application Serial No. 156,066. The inherent viscosity was about 0.2.

The resin couplers which we use are made by reacting these or similar polymers with couplers containing an amino radical. The preparation of suitable polymeric couplers is described below.

Example 7 Polymeric coupler having the recurring structure o o co Fifty grams of a vinyl acetate-maleic anhydride interpolymer (inherent viscosity of .25 g. per 100 cc. acetone=.2l) were dispersed with stirring in 750 cc. of dry acetone in an all glass outfit equipped with a stirrer and reflux condenser, protected from moisture by a calcium chloride tube. To the dope was added 100 g. of 2- amino-4,6-dichloro-5-methylphenol. The reaction mixture was heated on a steam bath with stirring for 1% hours. The tan solution was then poured with stirring into 8 liters of distilled water to which had been added 200 cc. of concentrated hydrochloric acid. The precipitate was filtered onto a Buchner funnel, washed on the funnel with distilled water and then stirred with two 3- liter portions of distilled water, filtering after each. It was given two reprecipitations from 600 cc. of acetone solution into water and hydrochloric acid as above with washing after each and finally washed chloride free with distilled water. The product was dried on a vacuum desiccator over calcium chloride under constant water pump vacuum. Yield was 88 g. Analysis: N, 3.25%; chlorine 15.55%.

Other resin couplers capable of forming cyan dye images on color development may be prepared from 2- aminophenol and polyacrylic anhydride, 2-aminophenol and styrene-maleic anhydride polymers, 2-amino-4,6- dichloro-S-methyl phenol and styrene-maleic anhydride interpolymers, and S-amino-l-naphthol and vinyl acetateialeic anhydride interpolymers.

Example 8 Polymeric coupler having the recurring structure In an outfit as above, 80 g. of styrene-maleic anhydride interpolymer (inherent viscosity=.18) were dispersed in 700 cc. of dry acetone. Two hundred grams of p-aminoa-benzoylacetanilide, washed in by 100 cc. of dry acetone were added and the reaction mixture heated on a steam bath for one hour with stirring, after which time a second viscous phase had separated. The reaction mixture was poured into 16 liters of distilled water containing 500 cc. of concentrated hydrochloric acid, with vigorous stirring and the gummy precipitate was stirred until it had turned friable. The product was filtered onto a Buchner funnel, Washed with water and given two reprecitations from acetone into 16 liters of distilled water containing 500 cc. of concentrated hydrochloric acid. After the second precipitation, it was washed chloride free and dried over r night in a vacuum desiccator over calcium chloride with constant Water pump vacuum. The product was dissolved in 900 cc. of acetone boiled with 150 grams of decolorizing carbon (Norite) and filtered. The filtrate was diluted with 9:1 acetone-distilled water (400 cc.

Polymeric coupler having the recurring structure (JO-CH2 in an outfit as above, 32 g. of styrene-maleic anhydride interpolymer (viscosity=.2l) were dispersed in 250 cc. of dry acetone. To the dope were added 62 g. of l-paminophenyl-3-methyl-5-pyrazolone, washed in by 70 cc. of dry acetone. The reaction mixture was heated on a steam bath with stirring for 35 minutes. The clear orange dope turned cloudy and the polymer then separated as a soft cake. Two hundred cc. of distilled water were added, stirred, and the supernatant liquid poured oil. Two hundred cc. of distilled water were added and the reaction heated on a steam bath to distill out the acetone. Three hundred cc. of 10% aqueous sodium hydroxide were added and steam bath heating continued with stirring, allowing any residual acetone to continue to distill away. The gelatinous mass slowly dispersed to give a gelatinous dope which, after a total of three hours of heating, gave a medium tan smooth dope. This was filtered, hot, through glass cloth. The filtrate was diluted with distilled water to 3 liters and made acid to Congo red with concentrated hydrochloric acid. A copious gelatinous precipitate formed. This was filtered onto paper by gravity and washed on the paper with distilled water. The precipitate was redissolved in 3 liters of distilled water by the addition of 10% aqueous sodium hydroxide, with stirring. Precipitation was then caused by acidification to Congo red with concentrated hydrochloric acid. The precipitate was filtered as above and washed until the filtrate was free from chloride. Resolution in dilute sodium hydroxide and reprecitation as above was repeated again washing until the filtrate Was chloride free. The product was then dried in a desiccator over calcium chloride with constant water pump vacuum. Yield: 58 grams.

Example 10 Polymeric coupler having the recurring structure In a 3-necked flask equipped with a nitrogen inlet, a mechanical stirrer, and a reflux condenser, protected from moisture by a calcium chloride tube, were placed 6.3 g. of polyacrylic anhydride, 20 g. of 2-amino-4,6- dichloro-5-methylphenol, and 100 cc. of dry acetone. The reaction mixture was heated on a steam bath with stirring while the air in the flask was displaced by dry nitrogen. In a short time an orange-brown dope was obtained. After one hour of heating, the dope was poured in a fine stream into 2 liters of distilled water containing cc. of concentrated hydrochloric acid. The friable precipitate obtained was Washed with distilled water and reprecipitated twice from 150 cc. of acetone into 2 liters of distilled water containing 50 cc. of concentrated hydrochloric acid. It was then washed free from chloride with distilled water and dried in a vacuum desiccator under constant water pump vacuum. The yield was 11.2 g.

Example 1] Polymeric coupler having the recurring structure OH OH1CHOHCH 1 (1.10 JJONH- Twenty grams of styrene-maleic anhydride interpolymer were dispersed under dry nitrogen in 200 cc. of dry acetone in a three-necked flask equipped with a mechanical stirrer, reflux condenser protected from moisture by a calcium chloride tube, and a nitrogen inlet. To the dope was added 25 g. of o-aminophenol. The reaction was heated on a steam bath under dry nitrogen. After twenty minutes, 100 cc. more of acetone were added, and after a total heating time of one hour, the reaction mixture was diluted with acetone and poured into 3 liters of distilled water containing cc. of concentrated hydrochloric acid. The precipitate was washed with water and then given two reprecipitations from acetone as above. The product was then washed free from chloride and dried in a vacuum desiccator under a constantly applied water pump vacuum. The yield was 25 g.

In the above preparations, an excess of the intermediate coupler was used to combine with the carboxyl that is formed during the course of the reaction. In order to reduce this amount of intermediate coupler to the theoretical mole to mole ratio, the procedures were modified. Examples of these modified procedures are given below:

Example 12 Polymeric coupler having the recurring structure 30 ('JONHCHzCHzNHC ln a 3-necked flask equipped with a reflux condenser protected from moisture by a calcium chloride tube and a mechanical stirrer, 322 g. of vinyl acetate-maleic anhydride interpolymer were dispersed in 2100 cc. of dry acetone. When doping was complete, 470 g. of l-hydroxy-4-chloro-2(fi-aminoethyl)naphthamide were added followed by 1120 cc. of dry acetone and 150 cc. of dry pyridine. The reaction mixture was heated with stirring on a steam bath. In 5 minutes it grew cloudy. After ten minutes a second phase separated and after 20 minutes a soft cake was present. After 35 minutes of heating 320 cc. of distilled water were added. With stirring, the cake redissolved. The dope was diluted with 1500 cc. of :1 by volume solution of acetone and distilled water and poured with stirring into 10 gallons of distilled water containing 1500 cc. of concentrated hydrochloric acid. The precipitate was filtered on to a Buchner funnel, washed on the funnel with distilled water, and again stirred with 10 gallons of distilled water. The solid was then dissolved in 5000 cc. of acetone. Three hundred and twenty grams of decolorizing carbon (Norite) were added and after being brought to a boil, the solution was filtered by suction through paper covered by a layer of filter aid (Special Filtrol). The filtrate was poured into 10 gallons of distilled water containing 750 cc. of concentrated hydrochloric acid. After stirring for minutes while the precipitate became friable, the solids were filtered, washed on the funnel with distilled water, and again stirred for 30 minutes in 10 gallons of distilled water. The product was filtered on to a funnel, Washed further with distilled water, and dried in a vacuum desiccator over calcium chloride under a constantly applied water pump vacuum. The yield was 581 g. Analysis: N=5.85%, chlorine:7.05%, acctyl=9.2%.

A portion of the above wet material was dried in an air oven at 40 C. A satisfactory product was obtained.

Example 13 Polymeric coupler having the recurring structure CH:CHCHCH One hundred and sixty grams of a styrene-malcic anhydride interpolymer were dispersed in 1600 cc. of dry acetone in an all-glass reflux outfit equipped with a mechanical stirrer and a reflux condenser protected from moisture by a calcium chloride tube. To the dope was added 220 g. of benzoylaceto-p-aminoanilide followed by 400 cc. of dry pyridine. The smooth dope obtained was heated on a steam bath with stirring for two hours during which time a soft second phase appeared. One hundred cc. of distilled water were added and with continued stirring a smooth dope was again obtained. This was diluted with 3 liters of 9:1 by volume acetone-distilled water and poured into 5 gallons of distilled water containing 1 liter of concentrated hydrochloric acid. The precipitate was stirred until it became friable and filtered on to a Buchner funnel where it was washed further with distilled water. The precipitate was then rcdispersed into 2500 cc. of acetone. Three hundred grams of Norite were added, and after being brought to a boil, the solution was filtered by suction through paper covered by a layer of filter aid. The acetone lost by evaporation was replaced, and the filtrate was precipitated in 5 gallons of distilled water containing 500 cc. of concentrated hydrochloric acid. The precipitate was filtered on to a funnel, washed on the funnel with distilled water, and then stirred for thirty minutes in 5 gallons of distilled Water. The product was dried in a vacuum desiccator over calcium chloride under a constantly applied water pump Polymeric coupler having the recurring structure N C-NHC O C3H OO-Cllz In an all-glass reflux outfit equipped with a reflux condenser protected from moisture by a calcium chloride tube, a mechanical stirrer, and a nitrogen inlet, g. of styrene-maleic anydride interpolymcr (inherent viscosity=0.21) were doped with stirring in 800 cc. of dry pyridine while a stream of dry nitrogen was passed over the reaction mixture. To the dope was added 163.8 g. of lp-aminophenyl-3-butyramido-5-benzoxypyrazole washed in by cc. of dry pyridine. The reaction mixture was heated on a steam bath with stirring under dry nitrogen for one hour and 15 minutes. The dope was diluted with 450 cc. of dry pyridine and precipitated in 18 liters of ether. The precipitate was filtered on to a Buchner funnel by suction, washed on the funnel with 2 liters of ether and then slurried in 4 liters of ether. It was again washed on the funnel with 2 liters of ether. The product was dried in the air to remove ether and twice slurried for twenty minutes with 8-liter portions of distilled water, each containing 200 cc. of concentrated hydrochloric acid, filtering by suction after each and washing on the funnel with distilled water. The product was stirred for 10 minutes with 8 liters of distilled water, filtered, further washed on the funnel with distilled water, and dried at 40 C. in an air oven. The yield was 173 g. containing 8.35% of nitrogen.

This polymer coupler dissolve with warming in diluted potassium carbonate solution during which time the benzoxyl group hydrolyzes off.

Other resin couplers capable of forming a magenta image upon coupling are the pyrazolyl styrene-maleic acid interpolymers described in Laakso and Allen U. S. Patent 2,646,421.

It will be understood that the examples included herein are illustrative only and that our invention is to be taken as limited only by the scope of the appended claims.

We claim:

1. A light-sensitive photographic emulsion comprising a mixture of hydrophilic, water-permeable colloid, silver halide sensitive to at least one region but less than all re ions of the visible spectrum, and a water-insoluble nondilfusing resin-coupler compound selected from those compounds having the recurring structure where R is selected from the class consisting of hydrogen, phenyl, alkyl, alkoxy, carboxyalkyl and acyloxy radicals, x and y are selected from the class consisting of 0 and l, R represents a color-forming group including an aryl group, capable of reacting with the oxidation product of a primary aromatic amino developing agent on photographic development, and R is selected from the class consisting of hydrogen and an alkyl radical, and the waterinsoluble salts of said compounds, and at least one separate mixture of hydrophilic water-permeable colloid. silver halide sensitive to a region of the visible spectrum different from that to which said first-mentioned silver halide is sensitive, and non-diffusing resin coupler having the formula stated above but having a color-forming group differing in chemical structure from said first-mentioned color-forming group and yielding a different dve with said developing agent. y

2. A light-sensitive mixed packet photographic emuls1o n compr1s1ng packets or discrete particles of hydrophIllC, water-permeable colloid, silver halide sensitive to at least one region but less than all regions of the visible spectrum, and salt of a non-diffusing resin-coupler compound of the recurring structure where R is selected from the class consisting of phenyl, carboxyalkyl and acyloxy radicals, x and y are selected from the class consisting of and 1, R represents a colorforming group including an aryl group, capable of reacting with the oxidation product of a primary aromatic amino developing agent on photographic development, and R is selected from the class consisting of hydrogen and an alkyl radical, and at least one separate set of packets or discrete particles of hydrophilic, water-permeable colloid, silver halide sensitive to a region of the visible spectrum different from that to which said firstmentioned silver halide is sensitive, and salt of a nondiffusing resin coupler having the formula stated above but having a color-forming group differing in chemical structure from said first-mentioned color-forming group and yielding a difierent dye with said developing agent.

3. A light-sensitive mixed packet photographic emulsion comprising packets or discrete particles of gelatin, silver halide sensitive to at least one region but less than all regions of the visible spectrum, and a salt of a nondiffusing resin-coupler compound of the recurring structure to ()H ins-R where R represents an o-hydroxy-substituted phenyl radical, and a separate setof packets or discrete particles of gelatin, silver halide sensitive to a region of the visible spectrum dilferent from that to which said first-mentioned silver halide is sensitive, and a salt of a non-difi'using resin coupler having the composition $11 ATH-QNHR where R represents the residue of a benzoylacetyl group.

4. The method of making a packet photographic emulsion which comprises mixing with a gelatino-silver halide emulsion a water-soluble salt of a resin-coupler compound of the recurring structure RI! RI! CH: -CH (--CHz),

( 1 12 )2 CO ONHR where R is selected from the class consisting of phenyl, carboxyalkyl and acyloxy radicals, x and y are selected from the class consisting of 0 and l, R represents a colorforming group including an aryl group, capable of reacting with the oxidation product of a primary aromatic amino developing agent, and R is selected from the class consisting of hydrogen and an alkyl radical, to form a solution of said resin-coupler in said emulsion, and mixing said solution with a packet-forming compound selected from the class consisting of methylmethacrylate-methacrylic acid copolymer, algin, carboxymethyl cellulose, cellulose sulfate, and alkaline earth metal salts, to form a dispersion of particles of gelatin, silver halide and resincoupler combination, in a gelatin matrix or continuous phase of gelatin.

5. The method of claim 4, which comprises additionally forming in the same way as said dispersion, at least one other dispersion of particles of gelatin, silver halide and resin-coupler combination in gelatin matrix, said lastmentioned silver halide being sensitive to a region of the visible spectrum different from that to which said firstmentioned silver halide is sensitive, and said last-mentioned resin-coupler combination being different in structure from said first-mentioned resin-coupler combination, and mixing said dispersions of particles with a hydrophilic colloid solution.

6. The method of making a packet photographic emulsion which comprises mixing with a gelatino-silver halide emulsion a watersoluble salt of a resin-coupler compound of the recurring structure where R is selected from the class consisting of phenyl, carboxyalkyl and acyloxy radicals, x and y are selected from the class consisting of 0 and 1, and R represents a color-forming group including an aryl group, capable of reacting with the oxidation product of a primary aromatic amino developing agent, to form a solution of said resin coupler in said emulsion, and mixing said emulsion with a water-soluble salt of methylmethacrylate-methacrylic acid copolymer to form a dispersion of particles of gelatin, silver halide and resin-coupler combination, in a gelatin matrix or continuous phase of gelatin.

7. The method of claim 6, which comprises additionally forming in the same way as said dispersion, at least one other dispersion of particles of gelatin, silver halide and resin-coupler combination in gelatin matrix, said lastmentioned silver halide being sensitive to a region of the visible spectrum different from that to which said firstmentioned silver halide is sensitive, and said last-mentioned resin-coupler combination being different in structure from said first-mentioned resin-coupler combination, and mixing said dispersions of particles with a hydrophilic colloid solution.

8. The method of making a packet photographic emulsion which comprises mixing with a gelatino-silver halide emulsion a water-soluble salt of a resin-coupler compound of the recurring structure where R is selected from the class consisting of phenyl, carboxyalkyl and acyloxy radicals, x and y are selected from the class consisting of O and 1, and R represents a color-forming group including an aryl group, capable of reacting with the oxidation product of a primary aromatic amino developing agent, to form a solution of said resin coupler in said emulsion, and then adding said solution and a solution of a calcium salt, slowly and with stirring to another solution of said calcium salt to form a dispersion of particles of gelatin, silver halide ad calcium salt of said resin coupler, in a gelatin matrix or continuous phase of gelatin.

9. The method of claim 8, which comprises additionally forming in the same way as said dispersion, at least one other dispersion of particles of gelatin, silver halide and resin-coupler combination in gelatin matrix, said lastmentioned silver halide being sensitive to a region of the visible spectrum different from that to which said firstmentioned silver halide is sensitive, and said last-mentioned resin-coupler combination being different in structure from said first-mentioned resin-coupler combination, and mixing said dispersions of particles with a hydrophilic colloid solution.

10. The method of making a mixed packet photographic emulsion which comprises mixing with a redsensitive gelatino silver halide emulsion the sodium salt of a resin coupler compound of the recurring structure where R represents an o-hydroxy-substituted phenyl radical, to form a solution of said resin coupler in said emulsion, mixing said solution with a solution of a watersoluble salt of methylmethacrylate-mcthacrylic acid copolymer to form a dispersion of particles of gelatin, redsensitive silver halide and resin-coupler combination in a gelatin matrix or continuous phase of gelatin, and forming in the same way as said first-mentioned dispersion a second dispersion of particles of gelatin, blue-sensitive silver halide and resin-coupler compound of the composition cmoHoH-cH where R represents the residue of a benzoyl acetyl group, in a gelatin matrix or continuous phase of gelatin, and mixing said dispersions of particles.

11. The method of making a mixed packet photographic emulsion which comprises mixing with a redsensitive gelatino-silver halide emulsion a water-soluble salt of a resin-coupler compound of the recurring structure in gelatin matrix and mixing said dispersions of particles. 12. A light-sensitive photographic emulsion comprising packets or discrete particles of gelatin, silver halide and salt of a non-diffusing resin-coupler compound of the recurring structure where R is selected from the class consisting of phenyl, carboxyalkyl and acyloxy radicals, x and y are selected from the class consisting of 0 and 1, R represents a colorforming group including an aryl group, capable of reacting with the oxidation product of a primary aromatic amino developing agent, and R is selected from the class consisting of hydrogen and an alkyl radical, said packets or discrete particles being dispersed in a matrix or continuous phase of hydrophilic water-permeable colloid.

13. A light-sensitive photographic emulsion comprising packets or discrete particles of gelatin, silver halide and salt of a non-diffusing resin-coupler compound of the recurring structure O CO- in M W where R represents the residue of a benzoyl acetyl group.

No references cited. 

1. A LIGHT SENSITIVE PHOTOGRAPHIC EMULSION COMPRISING A MIXTURE OF HYDROPHILIC, WATER-PERMEABLE COLLOID, SILVER HALIDE SENSITIVE TO AT LEAST ONE REGION BUT LESS THAN ALL REGIONS OF THE VISIBLE SPECTRUM, AND A WATER-INSOLUBLE NONDIFFUSING RESIN-COUPLER COMPOUND SELECTED FROM THOSE COMPOUNDS HAVING THE RECURRING STRUCTURE 